2-Chloro-1-(3-methyl-3-phenyl­cyclo­butyl)ethanone

The title compound, C₁₃H₁₅ClO, has a nonplanar conformation. The phenyl ring and chloro­acetaldehyde group are in cis positions. Mol­ecules are linked to one another by inter­molecular C—H...O inter­actions, forming a C(4) chain running parallel to the [001] direction. The cyclobutane ring is puckered, with a dihedral angle of 26.81 (13)°.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.030
• wR factor = 0.071
• Data-to-parameter ratio = 20.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.61 mm

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.88
           From the CIF: _reflns_number_total               2743
           Count of symmetry unique reflns         1499
           Completeness (_total/calc)            182.99%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1244
           Fraction of Friedel pairs measured     0.830
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

It has been shown that 3-substituted cyclobutane carboxylic acid deriatives have antidepressant activities and liquid crystal properties (Roger et al., 1977; Dehmlow & Schmidt, 1990;). Substituted α-haloketones, like title compound, are used for different purposes, especially in the synthesis of heterocyclic compounds (Gompper & Christmann, 1959; Çukurovalı et al., 2002). The extensive synthetic possibilies of this compound, due to the presence of active reaction sites, hold promise for the preparation of new heterocyclic chemicals. As a continuation of our investigations on the cyclobutane derivatives, a crystal structure determination of the title compound, (I), has been undertaken and the results are presented here.

In the crystal structure, the phenyl ring and chloroacetaldehyde group are in cis position with respect to the cyclobutane ring. Although close to being planar, the cyclobutane ring in (I) is more puckered than those in the literature [11.55 (3)°,Özdemir et al., 2004; 19.8 (3)°, Dinçer et al., 2004]. The C4/C3/C6 plane forms a dihedral angle of 26.81 (13)° with the C4/C5/C6 plane. However, the bond lengths and angles in the four-membered ring are normal (Allen et al., 1987). The C—Cl and C═O bond distances are 1.7692 (17) and 1.211 (2) Å, repectively, and these values are significantly shorter than those in the literature [1.807 (12) and 1.187 (16) Å, respectively; Demir et al., 2006].

In the crystal structure of (I), atom C1 in the molecule at (x, y, z) acts as hydrogen-bond donor to the O atom in the molecule at (-x + 1/2, y, z + 1/2), forming a C(4) (Bernstein et al., 1995) chain running parallel to the [001] direction and generated by the c-glide plane at x = 1/4 (Fig. 2). There are no other significant interactions in the crystal structure of (I).

Related literature

For related literature, see: Akhmedov et al. (1991); Allen et al. (1987); Bernstein et al. (1995); Dehmlow & Schmidt (1990); Demir et al. (2006); Dinçer et al. (2004); Farrugia (1997); Flack (1983); Gompper & Christmann (1959); Roger et al. (1977); Özdemir et al. (2004); Çukurovalı et al. (2002).

S2. Experimental

The synthesis of the title compound was realised according to the literature method (Akhmedov et al., 1991) with some modifications as given in the reaction sequence. The crystals which is suitable for X-ray analysis was obtained by the crystallization from n-hexane (yield 72%; m.p. 326 K). IR (ν, cm^-1): 1724 (C═O), 732 (–CH₂—Cl), 3049–3024 (Aromatics), 2980–2864 (Aliphatics); ¹H NMR (CDCl₃, p.p.m.): δ 1.54 (s, 3H, CH₃ on cyclobutane), 2.37 (m, 2H, –CH₂– in cyclobutane), 2.62 (m, 2H, –CH₂– in cyclobutane), 3.67 (q, j = 9.1 Hz, 1H, >CH–), 4.09 (s, 2H, –CH₂–), 7.13–7.34 (m, 5H, aromatics); ¹³C NMR (CDCl₆, p.p.m.): δ 47.02, 203.66, 37.51, 37.05, 38.83, 30.56, 151.03, 124.78, 128.58, 125.94.

S3. Refinement

H atoms were positioned geometrically and treated using a riding model, fixing the bond lengths at 0.93, 0.96, 0.97 and 0.98 Å for aromatic, methyl, methylene and methine H atoms, respectively. The displacement parameters of the H atoms were constrained to be U_iso(H)= 1.2U_eq(1.5U_eq for methyl) of the carrier atom. Refinement of the absolute structure parameter (Flack, 1983) yielded a value of -0.01 (5).

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures

	Fig. 1. An ORTEP-3 (Farrugia, 1997) drawing of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Part of the crystal structure of (I), showing a C(4) chain along [001]. For the sake of clarity, H atoms bonded to C atoms not involved in the motif shown have been omitted.
	Fig. 3. Reaction scheme for the preparation of (I).

2-Chloro-1-(3-methyl-3-phenylcyclobutyl)ethanone

Crystal data

C13H15ClO	F(000) = 472
Mr = 222.70	Dx = 1.267 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 6312 reflections
a = 9.4980 (9) Å	θ = 2.5–28.0°
b = 15.6393 (11) Å	µ = 0.30 mm^−1
c = 7.8578 (7) Å	T = 100 K
V = 1167.21 (17) Å^3	Prism, colorless
Z = 4	0.61 × 0.40 × 0.22 mm

Data collection

Stoe IPDS II diffractometer	2743 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2435 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.035
Detector resolution: 6.67 pixels mm^-1	θmax = 27.9°, θmin = 2.5°
ω scans	h = −12→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −20→20
Tmin = 0.885, Tmax = 0.944	l = −10→10
6736 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.030	w = 1/[σ^2(Fo^2) + (0.038P)^2 + 0.0689P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.071	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 0.20 e Å^−3
2743 reflections	Δρmin = −0.19 e Å^−3
137 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0052 (14)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1251 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.01 (5)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.41536 (4)	0.37951 (2)	0.10882 (5)	0.03443 (11)
O1	0.27620 (14)	0.54032 (7)	0.00821 (18)	0.0385 (3)
C1	0.43719 (18)	0.47994 (10)	0.2090 (2)	0.0304 (3)
H1A	0.4059	0.4754	0.3262	0.036*
H1B	0.5366	0.4940	0.2106	0.036*
C2	0.35801 (15)	0.55188 (9)	0.1242 (2)	0.0243 (3)
C3	0.39456 (16)	0.63806 (9)	0.19372 (19)	0.0234 (3)
H3	0.4005	0.6363	0.3182	0.028*
C4	0.52987 (14)	0.67903 (9)	0.1165 (2)	0.0253 (3)
H4A	0.6116	0.6759	0.1903	0.030*
H4B	0.5521	0.6591	0.0027	0.030*
C5	0.45381 (14)	0.76651 (9)	0.1207 (2)	0.0228 (3)
C6	0.31190 (15)	0.71696 (9)	0.13509 (19)	0.0227 (3)
H6A	0.2485	0.7397	0.2207	0.027*
H6B	0.2639	0.7093	0.0272	0.027*
C7	0.48815 (19)	0.81500 (11)	0.2856 (2)	0.0278 (4)
H7A	0.4785	0.7771	0.3810	0.042*
H7B	0.4244	0.8622	0.2984	0.042*
H7C	0.5830	0.8360	0.2806	0.042*
C8	0.46899 (18)	0.82486 (10)	−0.03045 (19)	0.0231 (3)
C9	0.58479 (18)	0.82191 (11)	−0.1395 (2)	0.0285 (3)
H9	0.6562	0.7825	−0.1200	0.034*
C10	0.5941 (2)	0.87746 (12)	−0.2769 (2)	0.0346 (4)
H10	0.6713	0.8743	−0.3494	0.041*
C11	0.4903 (2)	0.93721 (11)	−0.3071 (2)	0.0356 (4)
H11	0.4973	0.9743	−0.3992	0.043*
C12	0.3753 (2)	0.94139 (11)	−0.1987 (2)	0.0330 (4)
H12	0.3051	0.9818	−0.2175	0.040*
C13	0.36494 (19)	0.88556 (10)	−0.06253 (19)	0.0263 (3)
H13	0.2870	0.8886	0.0089	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0380 (2)	0.02533 (17)	0.0400 (2)	0.00003 (15)	0.0113 (2)	−0.0010 (2)
O1	0.0412 (7)	0.0304 (6)	0.0439 (7)	−0.0022 (5)	−0.0176 (6)	−0.0011 (5)
C1	0.0332 (8)	0.0289 (8)	0.0290 (7)	0.0035 (7)	0.0012 (7)	−0.0001 (7)
C2	0.0226 (6)	0.0268 (7)	0.0234 (6)	−0.0009 (5)	0.0016 (6)	0.0011 (7)
C3	0.0235 (7)	0.0248 (8)	0.0219 (7)	−0.0003 (6)	−0.0007 (6)	0.0025 (6)
C4	0.0211 (6)	0.0280 (7)	0.0269 (6)	0.0002 (5)	0.0015 (8)	0.0038 (8)
C5	0.0214 (6)	0.0259 (7)	0.0210 (6)	−0.0012 (5)	0.0005 (7)	0.0010 (7)
C6	0.0215 (6)	0.0258 (7)	0.0208 (7)	0.0004 (5)	−0.0001 (6)	0.0006 (6)
C7	0.0314 (9)	0.0302 (9)	0.0218 (7)	−0.0007 (7)	−0.0012 (7)	−0.0009 (6)
C8	0.0240 (8)	0.0239 (7)	0.0213 (7)	−0.0054 (6)	−0.0012 (6)	−0.0032 (6)
C9	0.0270 (8)	0.0316 (8)	0.0269 (7)	−0.0060 (7)	0.0016 (6)	−0.0037 (7)
C10	0.0377 (10)	0.0407 (9)	0.0253 (7)	−0.0155 (8)	0.0036 (7)	−0.0003 (7)
C11	0.0491 (11)	0.0310 (9)	0.0268 (8)	−0.0157 (8)	−0.0050 (8)	0.0043 (7)
C12	0.0428 (10)	0.0271 (8)	0.0290 (8)	−0.0048 (7)	−0.0109 (7)	0.0009 (7)
C13	0.0298 (8)	0.0245 (8)	0.0246 (7)	−0.0029 (6)	−0.0014 (6)	−0.0003 (6)

Geometric parameters (Å, º)

Cl1—C1	1.7692 (17)	C6—H6B	0.9700
O1—C2	1.211 (2)	C7—H7A	0.9600
C1—C2	1.509 (2)	C7—H7B	0.9600
C1—H1A	0.9700	C7—H7C	0.9600
C1—H1B	0.9700	C8—C13	1.393 (2)
C2—C3	1.495 (2)	C8—C9	1.395 (2)
C3—C6	1.5334 (19)	C9—C10	1.388 (2)
C3—C4	1.559 (2)	C9—H9	0.9300
C3—H3	0.9800	C10—C11	1.379 (3)
C4—C5	1.5475 (19)	C10—H10	0.9300
C4—H4A	0.9700	C11—C12	1.386 (3)
C4—H4B	0.9700	C11—H11	0.9300
C5—C8	1.505 (2)	C12—C13	1.385 (2)
C5—C7	1.536 (2)	C12—H12	0.9300
C5—C6	1.5589 (19)	C13—H13	0.9300
C6—H6A	0.9700
C2—C1—Cl1	114.01 (12)	C5—C6—H6A	113.8
C2—C1—H1A	108.7	C3—C6—H6B	113.8
Cl1—C1—H1A	108.7	C5—C6—H6B	113.8
C2—C1—H1B	108.7	H6A—C6—H6B	111.1
Cl1—C1—H1B	108.7	C5—C7—H7A	109.5
H1A—C1—H1B	107.6	C5—C7—H7B	109.5
O1—C2—C3	123.96 (13)	H7A—C7—H7B	109.5
O1—C2—C1	122.75 (14)	C5—C7—H7C	109.5
C3—C2—C1	113.26 (14)	H7A—C7—H7C	109.5
C2—C3—C6	119.78 (13)	H7B—C7—H7C	109.5
C2—C3—C4	114.81 (13)	C13—C8—C9	118.07 (15)
C6—C3—C4	88.53 (11)	C13—C8—C5	119.21 (14)
C2—C3—H3	110.6	C9—C8—C5	122.71 (15)
C6—C3—H3	110.6	C10—C9—C8	120.48 (17)
C4—C3—H3	110.6	C10—C9—H9	119.8
C5—C4—C3	88.29 (10)	C8—C9—H9	119.8
C5—C4—H4A	113.9	C11—C10—C9	120.80 (17)
C3—C4—H4A	113.9	C11—C10—H10	119.6
C5—C4—H4B	113.9	C9—C10—H10	119.6
C3—C4—H4B	113.9	C10—C11—C12	119.31 (16)
H4A—C4—H4B	111.1	C10—C11—H11	120.3
C8—C5—C7	110.25 (11)	C12—C11—H11	120.3
C8—C5—C4	118.32 (15)	C13—C12—C11	120.08 (18)
C7—C5—C4	110.82 (14)	C13—C12—H12	120.0
C8—C5—C6	116.20 (13)	C11—C12—H12	120.0
C7—C5—C6	111.58 (13)	C12—C13—C8	121.26 (16)
C4—C5—C6	88.04 (10)	C12—C13—H13	119.4
C3—C6—C5	88.80 (10)	C8—C13—H13	119.4
C3—C6—H6A	113.8
Cl1—C1—C2—O1	6.8 (2)	C4—C5—C6—C3	19.01 (13)
Cl1—C1—C2—C3	−171.24 (11)	C7—C5—C8—C13	−75.72 (17)
O1—C2—C3—C6	8.6 (2)	C4—C5—C8—C13	155.30 (13)
C1—C2—C3—C6	−173.33 (13)	C6—C5—C8—C13	52.5 (2)
O1—C2—C3—C4	−94.80 (19)	C7—C5—C8—C9	103.18 (17)
C1—C2—C3—C4	83.25 (17)	C4—C5—C8—C9	−25.8 (2)
C2—C3—C4—C5	141.38 (13)	C6—C5—C8—C9	−128.62 (16)
C6—C3—C4—C5	19.00 (12)	C13—C8—C9—C10	−0.8 (2)
C3—C4—C5—C8	−137.59 (13)	C5—C8—C9—C10	−179.69 (15)
C3—C4—C5—C7	93.69 (14)	C8—C9—C10—C11	0.8 (3)
C3—C4—C5—C6	−18.69 (12)	C9—C10—C11—C12	−0.1 (3)
C2—C3—C6—C5	−136.82 (14)	C10—C11—C12—C13	−0.5 (3)
C4—C3—C6—C5	−18.86 (12)	C11—C12—C13—C8	0.5 (2)
C8—C5—C6—C3	139.81 (13)	C9—C8—C13—C12	0.2 (2)
C7—C5—C6—C3	−92.64 (13)	C5—C8—C13—C12	179.10 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1^i	0.97	2.46	3.244 (2)	137

Symmetry code: (i) −x+1/2, y, z+1/2.